Defensive publication

ABSTRACT

THIS DISCLOSURE RELATES TO NOVEL DYES AND PHOTOGRAPHIC MATERIALS. IN ONE ASPECT IT RELATES TO PHOTOGRAPHIC SILVER HALIDE EMULSIONS SPECTRALLY SENSITIZED WITH CYANINE AND HEMICYANINE DYES HAVING A TERTIARY AMINOALKYL GROUP SUBSTITUTED ON THE HETEROCYCLIC NITROGEN ATOM OF THE BASIC NUCLEUS. IN ONE PREFERRED EMBODIMENT, UNSYMMETRICAL CYANINE DYES ARE PROVIDED COMPRISING FIRST AND SECOND NUCLEI JOINED BY A LINKAGE SELECTED FROM A TRIMETHINE LINKAGE AND A PENTAMETHINE LINKAGE; THE FIRST NUCLEUS BEING A NITROGEN-CONTAINING BASIC HETEROCYCLIC NUCLEUS OF THE TYPE USED IN CYANINE DYES, SAID HETERO-NITROGEN ATOM HAVING ATTACHED THERETO A TERTIARY AMINOALKYL GROUP; AND THE SECOND NEUCLEUS BEING A NITROGEN-CONTAINING BASIC HETEROCYCLIC NUCLEUS OF THE TYPE USED IN CYANINE DYES, SAID HETERONITROGEN ATOM HAVING ATTACHED THERETO AN ALKYL GROUP. HIGHLY USEFUL PHOTOGRAPHIC SPECTRAL SENSITIZING SYMMETRICAL CYANINES AND HEMICYANINES ARE ALSO PROVIDED. TYPICAL USEFUL DYES HAVE ONE OF THE FOLLOWING FORMULAS:   WHEREIN N REPRESENTS 1 TO 3, K AND J EACH REPRESENTS 1 OR 2; Z1 AND Z2 EACH REPRESENTS THE NON-METALLIC ATOMS REQUIRED TO COMPLETE A 5- TO 6-MEMBERED NITROGEN-CONTAINING BASIC HETEROCYCLIC NUCLEUS; R1 REPRESENTS AN ALKYLENE GROUP CONTAINING FROM 2 TO 6 CARBON ATOMS; R2 AND R3 EACH REPRESENTS A MEMBER OF THE GROUP CONSISTING OF ALKYL, ARYL AND, R2 OR R3 TAKEN TOGETHER, REPRESENT THE ATOMS TO COMPLETE, WITH THE NITROGEN ATOM TO WHICH THEY ARE ATTACHED, A HETEROCYCLIC NUCLEUS CONTAINING FROM 5 TO 6 ATOMS; R4 REPRESENTS AN ALKYL GROUP OR AR ARYL GROUP; R5 REPRESENTS HALOGEN, NITRO, CYANO OR AMINO; Z REPRESENTS THE ATOMS REQUIRED TO COMPLETE A BASIC HETEROCYCLIC NUCLEUS; AND X REPRESENTS AN ACID ANION. A TYPICAL USEFUL DYE IS 5-CHLORO-1,3&#39;&#39;-DIETHYL-3-(2-MORPHOLINOETHYL) BENZIMIDAZOLOTHIACARBOCYANINE IODIDE.

UNITED STATES PATENT OFFICE Published at the request of the applicant orowner in accordance with the Notice of Dec. 16, 1969, 869 0.6. 687. Theabstracts of Defensive Publication applications are identified bydistinctly numbered series and are arranged chronologically. The headingof each abstract indicates the number of pages of specification.including claims and sheets of drawings contained in the application asoriginally filed. The files of these applications are available to thepublic for inspection and reproduction may be purchased for 30 cents asheet.

Defensive Publication applications have not been examined as to themerits of alleged invention. The Patent Oflice makes '10 assertion us tothe novelty of the disclosed subject matter.

PUBLISHED AUGUST 31, 1971 T889,016 PHOTOGRAPHIC MATERIALS Earl J. VanLare, Rochester, and Arthur Fumia, Jr., Hilton, N.Y. (both of KodakPark, Rochester, NY. 14650) Filed Sept. 25, 1970, Ser. No. 75,786 lint.Cl. G03c 1/14 U.S. Cl. 96-127 No Drawing. 39 Pages Specification Thisdisclosure relates to novel dyes and photographic materials. In oneaspect it relates to photographic silver halide emulsions spectrallysensitized with cyanine and hemicyanine dyes having a tertiaryaminoalkyl group substituted on the heterocyclic nitrogen atom of thebasic nucleus. In one preferred embodiment, unsymmetrical cyanine dyesare provided comprising first and second nuclei joined by a linkageselected from a trimethine linkage and a pentamethine linkage; the firstnucleus being a nitrogen-containing basic heterocyclic nucleus of thetype used in cyanine dyes, said hetero-nitrogen atom having attachedthereto a tertiary aminoalkyl group; and the second nucleus being anitrogen-containing basic heterocyclic nucleus of the type used incyanine dyes, said heteronitrogen atom having attached thereto an alkylgroup. Highly useful photographic spectral sensitizing symmetricalcyanines and hemicyanines are also provided. Typical useful dyes haveone of the following formulas:

wherein n represents 1 to 3, k and 1' each represents 1 or 2; Z and Zeach represents the non-metallic atoms required to complete a 5- to6-membered nitrogen-containing basic heterocyclic nucleus; R representsan alkylene group containing from 2 to 6 carbon atoms; R and R eachrepresents a member of the group consisting of alkyl, aryl and, R or Rtaken together, represent the atoms to complete, With the nitrogen atomto which they are attached, a heterocyclic nucleus containing from 5 to6 atoms; R represents an alkyl group or an aryl group; R representshalogen, nitro, cyano or amino; Z represents the atoms required tocomplete a basic heterocyclic nucleus; and X represents an acid anion. Atypical useful dye is S-chloro-1,3'-diethyl-3-(2morpholinoethyl)benzimidazolothiacarbocyanine iodide.

